US7946022B2 - Copper alloy for electronic machinery and tools and method of producing the same - Google Patents

Copper alloy for electronic machinery and tools and method of producing the same Download PDF

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US7946022B2
US7946022B2 US11/478,292 US47829206A US7946022B2 US 7946022 B2 US7946022 B2 US 7946022B2 US 47829206 A US47829206 A US 47829206A US 7946022 B2 US7946022 B2 US 7946022B2
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copper alloy
mass
alloy material
precipitate
layer
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US20070015001A1 (en
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Takeo Uno
Chikahito Sugahara
Kuniteru Mihara
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Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
    • H01L21/4814—Conductive parts
    • H01L21/4821—Flat leads, e.g. lead frames with or without insulating supports
    • H01L21/4842—Mechanical treatment, e.g. punching, cutting, deforming, cold welding
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
    • H01L23/49582—Metallic layers on lead frames
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/4998—Combined manufacture including applying or shaping of fluent material
    • Y10T29/49988—Metal casting
    • Y10T29/49991—Combined with rolling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12472—Microscopic interfacial wave or roughness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
    • Y10T428/12507—More than two components
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
    • Y10T428/12514—One component Cu-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12687—Pb- and Sn-base components: alternative to or next to each other
    • Y10T428/12694—Pb- and Sn-base components: alternative to or next to each other and next to Cu- or Fe-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12771—Transition metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component
    • Y10T428/1291—Next to Co-, Cu-, or Ni-base component

Definitions

  • the present invention relates to a copper alloy improved in platability with metals.
  • Copper alloys used in electronic machinery and tools are given various kinds of metal plating, seeking to impart more functionality thereto.
  • lead frames for example, they are given Ag plating for wire bonding, Cu plating as a foundation for the said Ag plating, and solder plating for mounting on boards.
  • plated lead frames prepared by giving metal plating throughout the surface of lead frames after forming lead by etching or presswork.
  • the metal plating given therein includes Pd plating, and Ni plating as a foundation thereof.
  • the Cu plating as a foundation is exposed in areas to which Ag plating is not given, and when it is heated in a packaging process, an oxidation film on the lead frame surface is formed.
  • anomalous precipitation, for example, porous precipitation, of the Cu plating causes formation of oxide film inferior in adhesiveness on the lead frame surface, to result in lowering of adhesion between a mold resin and lead frames.
  • the problem occurs that, when soldering onto boards is carried out, packages become cracked in a reflowing furnace.
  • a copper alloy having an excellent platability with metals and causing neither anomalous precipitation of plating metals nor lowering of adhesiveness of oxidation film can be provided for use in electronic machinery and tools.
  • Copper alloys are generally produced by using appropriate combinations of steps, such as casting, hot rolling, cold rolling, buff polishing and annealing, and undergo various types of plastic working in the process of production. As a result of the plastic working, a work affected layer and a plastic deformation layer, showing finer crystalline structure than those in the bulk copper alloy (or inner part of the copper alloy), are formed in the copper alloy surface layer.
  • “work affected layer” refers to a non-uniform microcrystalline structure (for example, amorphous, or the grain size of less than 0.2 ⁇ m) which is formed in the surface layer of a copper alloy underlying various types of plastic deformation processing as stated above, and is constituted of a Beilby layer (upper layer) and a microcrystalline layer (lower layer).
  • the Beilby layer has an amorphous structure, while the microcrystalline layer has a very fine crystalline aggregate texture.
  • the plastic deformation layer has a crystalline aggregate texture that the crystal grains therein is coarser than those in the microcrystalline layer and their sizes (for example, from about 0.2 to 3.0 ⁇ m) approach gradually sizes of crystal grains in the bulk copper alloy (or inner part of the copper alloy) (for example, from about 3.0 to 10.0 ⁇ m).
  • the present copper alloy for electronic machinery and tools is a copper alloy having in its surface layer a nonuniform and fine work affected layer controlled so as to have a thickness of 0.2 ⁇ m or below by removing treatment.
  • a nonuniform and fine work affected layer controlled so as to have a thickness of 0.2 ⁇ m or below by removing treatment.
  • the present invention provides an improvement in the platability of a copper alloy by reducing the thickness of a work affected layer present in the copper alloy surface layer to 0.2 ⁇ m or below, and exerts its effect on various types of copper alloys differing in alloy composition and property.
  • the present invention can also ensure prevention of anomalous precipitation in solder plating, Ni plating or else as in the cases of Ag plating and Cu plating, thereby offering an excellent platability.
  • Lead frames, terminals and connectors using the present copper alloy for electronic machinery and tools have satisfactory yields because the troubles ascribable to the platability of a copper alloy don't occur in their respective producing methods, and ensure high reliability in not only packaging and onboard-mounting processes but also at the use stage subsequent thereto.
  • FIG. 1 is a cross-sectional photograph of a copper alloy under SIM observation.
  • FIG. 2 is a schematic diagram depicting a cross-section of a copper alloy comprising a work affected layer 1 and a plastic deformation layer 2 .
  • the present invention requires that the work affected layer has a thickness reduced to the limit of no effect on crystallinity under precipitation of the metal plating. Specifically, it is preferable that the thickness be adjusted to 0.2 ⁇ m or below. For uses requiring high reliability in particular, it is more preferable to adjust the thickness of the work affected layer to 0.05 ⁇ m or below.
  • Examples of metal plating which can be given to the copper alloy of the present invention include Ag plating, Cu plating, solder plating, Sn plating and Ni plating.
  • the present invention is especially preferable for application to Ag plating or Cu plating given to copper alloys for uses in such as lead frames, terminals and connectors.
  • Examples of a copper alloy usable as the copper alloy of the present invention include not only Cu—Sn-series and Cu—Zn-series alloys of solid-solution type but also Cu—Cr—Sn-series, Cu—Cr-series, Cu—Ni—Si-series, Cu—Fe—P-series and Cu—Ni—Sn-series copper alloys of precipitate type.
  • these alloys those especially suitable for application of the present invention are Cu—Cr—Sn-series and Cu—Ni—Si-series copper alloys used for multi-pin lead frames with narrow lead pitches.
  • the chemical composition thereof is within the following range.
  • Chromium (Cr) is an addition element causing precipitation in copper and thereby enhancing strength of the copper alloy.
  • Cr is added in a too small amount, it has little effect on the strength enhancement; while, when the amount is too large, the effect of Cr addition reaches a level of saturation. Therefore, the preferable range in the present invention is from 0.05 to 0.5% by mass. In this range, the range of 0.1 to 0.45% by mass is more preferable, and the range of 0.2 to 0.4% by mass is far more preferable.
  • Tin (Sn) and zinc (Zn) are addition elements forming solid solutions in copper, and providing solid-solution reinforcement and further having the effect of remarkably increasing the strength in the subsequent cold working.
  • the addition of these elements in a small amount produces little effect, while their addition in a large amount impairs electric conductivity.
  • the Sn content is preferably 0.05 to 2.0% by mass
  • the Zn content is preferably 0.05 to 1.0% by mass.
  • the Sn content is more preferably from 0.1 to 0.5% by mass, far more preferably from 0.2 to 0.4% by mass
  • the Zn content is more preferably from 0.1 to 0.5% by mass, far more preferably from 0.15 to 0.3% by mass.
  • silicon (Si), or zirconium (Zr), or both may be added to the Cu—Cr—Sn-series copper alloy.
  • the Si is an addition element forming a Cr—Si precipitate in combination with Cr, and enhancing copper alloy strength by complex precipitation of Cr and Cr—Si.
  • the addition of Si in a too small amount produces little effect, while its addition in a too large amount impairs electric conductivity.
  • the Si content is preferably adjusted to the range of 0.01 to 0.5% by mass, more preferably 0.05 to 0.4% by mass, far more preferably 0.1 to 0.3% by mass.
  • Zr is an addition element causing precipitation in copper and thereby enhancing copper alloy strength.
  • the addition of Zr in a too small amount produces little effect, while the effect of Zr addition reaches saturation when the amount of Zr is too large.
  • the Zr content is preferably adjusted to the range of 0.01 to 0.5% by mass, more preferably 0.05 to 0.4% by mass, far more preferably 0.1 to 0.3% by mass.
  • the total amount of Si content and Zr content is preferably in a range of 0.01 to 0.5% by mass.
  • the chemical composition thereof is within the following range.
  • Ni and Si are addition elements forming a Ni—Si precipitate by control of the addition ratio between Ni and Si, and providing precipitation reinforcement to increase the copper alloy strength.
  • the Ni content is preferably from 2.0 to 4.5% by mass, more preferably from 2.0 to 4.0% by mass, far more preferably from 2.5 to 4.0% by mass.
  • the degree of reinforcement becomes the maximum when the addition amount of Si is about one-fifth the addition amount of Ni. Accordingly, the Si content is preferably adjusted to a range of 0.25 to 1.0% by mass, more preferably 0.4 to 0.9% by mass, far more preferably 0.4 to 0.8% by mass, especially far more preferably 0.5 to 0.8% by mass.
  • Mg, Ag, Mn, Sn and Zn may be added to the Cu—Ni—Si series copper alloy.
  • Magnesium (Mg) is an addition element increasing copper alloy strength by forming a solid solution or causing precipitation in copper.
  • the addition of Mg in a too small amount has little effect, and that in a too large amount lowers hot workability of ingot.
  • the Mg content is preferably from 0.05 to 0.3% by mass, more preferably from 0.05 to 0.15% by mass, furthermore preferably from 0.1 to 0.2% by mass, especially preferably from 0.13 to 0.17% by mass.
  • Silver (Ag) is an addition element increasing copper alloy strength by forming a solid solution in copper.
  • the addition of Ag in a too small amount produces little effect, while that in a too large amount saturates the effect of Ag addition, and causes a rise in cost. Therefore, the Ag content is preferably 0.005 to 0.2% by mass, more preferably 0.005 to 0.1% by mass, further preferably 0.01 to 0.1% by mass, and far more preferably 0.02 to 0.05% by mass.
  • Manganese (Mn) is an addition element improving hot workability of ingot.
  • the addition of Mn in a too small amount produces little effect, while that in a too large amount impairs electric conductivity.
  • the Mn content is preferably 0.005 to 0.2% by mass, more preferably 0.005 to 0.1% by mass, further preferably 0.01 to 0.15% by mass, far more preferably 0.07 to 0.12% by mass.
  • Sn and Zn are elements forming solid solutions in copper, and providing solid-solution reinforcement and further having the effect of remarkably increasing the strength in the subsequent cold working.
  • the addition of these elements in a too small amount produces little effect, while their addition in a too large amount impairs electric conductivity of the copper alloy.
  • the Sn content is preferably limited to 0.05 to 2.0% by mass or below, and the Zn content is preferably limited to 0.05 to 1.0% by mass.
  • the Sn content is more preferably from 0.05 to 1.0% by mass, far more preferably from 0.1 to 0.2% by mass, and the Zn content is more preferably from 0.1 to 0.7% by mass.
  • the total amount of contents of Ag, Mg, Mn, Sn, Zn is preferably in a range of 0.005 to 2.0% by mass.
  • methods of removal by chemical dissolving treatment, electrochemical dissolving treatment and physical treatment such as sputtering can be applied in removing the work affected layer of the copper alloy.
  • physical treatment such as sputtering
  • the method of removal by chemical or electrochemical dissolving treatment or heat treatment is suitable as an industrial method.
  • an acid solution containing a combination of acid and oxidizer In the chemical dissolving treatment, it is possible to use an acid solution containing a combination of acid and oxidizer.
  • sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid or phosphoric acid can be used as the acid
  • hydrogen peroxide, chromate or persulfate can be used as the oxidizer.
  • the combination of sulfuric acid and hydrogen peroxide is preferred over the others from the viewpoint of the dissolution speed, consideration for the environmental aspect and workability.
  • anodic electrolysis in an acidic solution can be utilized, wherein an electrolytic solution prepared by adding an inorganic acid like chromic acid to phosphoric acid or sulfuric acid is applicable.
  • Electrolytic solutions containing phosphoric acid are suitable for the copper alloys because of their proven track record and excellent polishing effect.
  • heating in a reducing- or inert-atmosphere furnace can be utilized. More specifically, batch heating in an annealing furnace or continuous heating in a continuous annealing furnace is applicable so long as the heating temperature and the heating time are appropriately combined. In order to prevent surface oxidation of copper alloy during the removal treatment, the heating in a reducing atmosphere, such as the atmosphere of hydrogen, is advisable. So the batch heating in such as a bell-type furnace is suitable from the viewpoint of stability for oxygen concentration during the heat treatment.
  • An inspection of the work affected layer of the present copper alloy is made by the profile of the surface layer of the copper alloy being observed under magnification.
  • the structures it is advantageous for the structures to be observed in a state that they are magnified about 10,000 times with an electron microscope, and the use of such an observation device as SIM or FE-SEM is especially favorable.
  • FIGS. 1 and 2 the cross-sectional structure of the copper alloy is explained.
  • FIG. 1 is a cross-sectional photograph of a copper alloy under SIM observation.
  • FIG. 2 is a schematic diagram depicting a cross-section of a copper alloy comprising a work affected layer 1 and a plastic deformation layer 2 .
  • the work affected layer 1 is made up of a Beilby layer 3 (upper layer) and a microcrystalline layer 4 (lower layer).
  • the Beilby layer 3 has an amorphous texture
  • the microcrystalline layer 4 has a very fine crystalline aggregate texture.
  • the plastic deformation layer 2 present underneath the work affected layer 1 is coarser in crystal grains than the microcrystalline layer and, as shown in FIG. 1 , the work affected layer 1 (the area enclosed with a broken line) is clearly different in crystalline structure from the plastic deformation layer 2 . So these two layers are readily distinguishable.
  • the work affected layer varies in the amount formed according to the degree of processing, so there are cases in which the thickness thereof varies within the field of view or in comparison among different observation spots when it is observed under magnification by microscope observation. Therefore, a thickness of the work affected layer is measured at its thickest position within the field of observation under magnification, and the mean of thickness values measured at 5 different observation spots is defined as the thickness of the work affected layer.
  • Copper alloys having chemical compositions shown in Table 1 were made into 0.15-mm thick copper alloy sheets by undergoing casting, rolling, buff polishing and annealing in succession. These copper alloy sheets were each given degreasing treatment and pickling treatment, and then subjected to treatment for removal of their respective work affected layers by chemical dissolution. Each of the thus treated materials was coated with Ag plating, and Ag platability was evaluated.
  • the degreasing treatment was performed by cathodic electrolysis for 30 seconds in a degreasing solution, which contained 60 g/l of Cleaner 160S (trade name, produced by Meltex Inc.) and was kept at a temperature of 60° C., under a current density of 2.5 A/d m 2 .
  • the pickling treatment was performed at room temperature by immersion for 30 seconds in an acid pickling solution containing 100 g/l of sulfuric acid.
  • Each of the work affected layers underwent removal treatment by immersion in an aqueous solution containing 100 g/l of sulfuric acid and 15 g/l of hydrogen peroxide at room temperature.
  • five specimens of each copper alloy were prepared for examples of the present invention so that their individual work affected layers after the removal treatment had different thicknesses of 0, 0.02, 0.05, 0.1 and 0.2 ⁇ m, respectively; while one specimen of each copper alloy was prepared for a comparative example so that its work affected layer after the removal treatment had the thickness of 0.3 ⁇ m.
  • the Ag plating was performed at room temperature in an Ag plating bath containing 55 g/l of silver potassium cyanide, 75 g/l of potassium cyanide, 10 g/l of potassium hydroxide and 25 g/l of potassium carbonate under a current density of 1.0 A/dm 2 until the plating thickness reached 3 ⁇ m.
  • each copper alloy specimen As to the Ag platability of each copper alloy specimen, the Ag-plated surface of each specimen was observed under a microscope of 450 magnifications (made by Keyence Corporation), and the number of projecting anomalous precipitates formed on the Ag-plated surface was counted. The condition of each Ag-plated surface was rated as “ ⁇ ” when the number of anomalous precipitates per unit area was smaller than 5 per mm 2 , it was rated as “ ⁇ ” when the number was from 5 to 10 per mm 2 , and it was rated as “ ⁇ ” when the number was greater than 10 per mm 2 .
  • Example 2 Ag plating was performed in the same manner as in Example 1, except that electrolytic dissolution was used as the method of removing the work affected layer of each copper alloy, and the Ag platability was evaluated using the same criteria as in Example 1.
  • each copper alloy was removed by anodic electrolysis in an aqueous solution containing 700 g/l of phosphoric acid at room temperature under a current density of 10 A/dm 2 .
  • five specimens of each copper alloy were prepared for examples of the present invention so that their individual work affected layers after the removal treatment had thicknesses of 0, 0.02, 0.05, 0.1 and 0.2 ⁇ m, respectively; while one specimen of each copper alloy was prepared for a comparative example so that its work affected layer after the removal treatment had the thickness of 0.3 ⁇ m.
  • Example 2 Ag plating was performed in the same manner as in Example 1, except that heat treatment was used as the method of removing the work affected layer of each copper alloy, and the Ag platability was evaluated using the same criteria as in Example 1.
  • each copper alloy was removed by heat treatment of 2 hours in a heating furnace with a reducing atmosphere of hydrogen.
  • five specimens of each copper alloy were prepared for examples of the present invention so that their individual work affected layers after the removal treatment had thicknesses of 0, 0.02, 0.05, 0.1 and 0.2 ⁇ m, respectively; while one specimen of each copper alloy was prepared for a comparative example so that its work affected layer after the removal treatment had the thickness of 0.3 ⁇ m.
  • the heat-treatment temperatures were set at 600, 585, 565, 540, 500 and 450° C., respectively.
  • Copper alloys having chemical compositions shown in Table 1 were made into 0.15-mm thick copper alloy sheets by undergoing casting, rolling and annealing in succession. These copper alloy sheets were each given degreasing treatment and pickling treatment, and then subjected to treatment for removal of their respective work affected layers by chemical dissolution. Each of the thus treated materials was coated with Cu plating, and Cu platability was evaluated.
  • the degreasing treatment was performed by cathodic electrolysis for 30 seconds in a degreasing solution, which contained 60 g/l of Cleaner 160S (trade name, produced by Meltex Inc.) and was kept at a temperature of 60° C., under a current density of 2.5 A/dm 2 .
  • the pickling treatment was performed at room temperature by immersion for 30 seconds in an acid pickling solution containing 100 g/l of sulfuric acid.
  • Each of the work affected layers underwent removal treatment by immersion in an aqueous solution containing 100 g/l of sulfuric acid and 15 ⁇ l of hydrogen peroxide at room temperature.
  • five specimens of each copper alloy were prepared for examples of the present invention so that their individual work affected layers after the removal treatment had different thicknesses of 0, 0.02, 0.05, 0.1 and 0.2 ⁇ m, respectively; while one specimen of each copper alloy was prepared for a comparative example so that its work affected layer after the removal treatment had the thickness of 0.3 ⁇ m.
  • the Cu plating was performed at a liquid temperature of 45° C. in an Cu plating bath containing 65 g/l of copper cyanide, 110 g/l of potassium cyanide and 7.5 g/l of potassium carbonate under a current density of 1.5 A/dm 2 until the plating thickness reached 0.1 ⁇ m.
  • the Cu platability of each copper alloy was evaluated by tape peel testing. After the Cu-plating, a sample was cut to a length of 30 mm and a width of 10 mm from each of the copper alloy sheets, and heated using a hot plate for 7 minutes at 350° C. in the atmosphere. On the oxide film thus formed on the sample surface, an adhesive tape (631S made by Teraoka Seisakusho Co., Ltd.) was stuck, and then peeled off. At this peeling-off, cases in which almost no exfoliation was observed were rated as “ ⁇ ”, cases in which exfoliation was observed in some spots were rated as “ ⁇ ”, and cases in which exfoliation was observed in at least one-half the total area were rated as “ ⁇ ”.
  • Cu plating was performed in the same manner as in Example 4, except that electrolytic dissolution was used as the method of removing the work affected layer of each copper alloy, and the Cu platability was evaluated using the same criteria as in Example 4.
  • each copper alloy was removed by anodic electrolysis in an aqueous solution containing 700 g/l of phosphoric acid at room temperature under a current density of 10 A/dm 2 .
  • five specimens of each copper alloy were prepared for examples of the present invention so that their individual work affected layers after the removal treatment had thicknesses of 0, 0.02, 0.05, 0.1 and 0.2 ⁇ m, respectively; while one specimen of each copper alloy was prepared for a comparative example so that its work affected layer after the removal treatment had the thickness of 0.3 ⁇ m.
  • Cu plating was performed in the same manner as in Example 4, except that heat treatment was used as the method of removing the work affected layer of each copper alloy, and the Cu platability was evaluated using the same criteria as in Example 4.
  • each copper alloy was removed by heat treatment of 2 hours in a heating furnace with a reducing atmosphere of hydrogen.
  • five specimens of each copper alloy were prepared for examples of the present invention so that their individual work affected layers after the removal treatment had thicknesses of 0, 0.02, 0.05, 0.1 and 0.2 ⁇ m, respectively; while one specimen of each copper alloy was prepared for a comparative example so that its work affected layer after the removal treatment had the thickness of 0.3 ⁇ m.
  • the heat-treatment temperatures were set at 600, 585, 565, 540, 500 and 450° C., respectively.
  • the exfoliation area of the oxidation film formed after Cu-plating was small in every example of the present invention.
  • the thickness of the work affected layer was thinner than or equal to 0.05 ⁇ m, the exfoliation area of the oxide film was very small and the Cu platability was particularly excellent.
  • the copper alloy of the present invention is excellent in platability. Therefore, the copper alloy is suitable for use in, for example, parts of electronic machinery and tools, such as semiconductor lead frames, terminals and connectors.
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